US9005698B2 - Piezoelectric thin film process - Google Patents
Piezoelectric thin film process Download PDFInfo
- Publication number
- US9005698B2 US9005698B2 US13/340,093 US201113340093A US9005698B2 US 9005698 B2 US9005698 B2 US 9005698B2 US 201113340093 A US201113340093 A US 201113340093A US 9005698 B2 US9005698 B2 US 9005698B2
- Authority
- US
- United States
- Prior art keywords
- sol gel
- gel layer
- ambient
- torr
- wafer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active, expires
Links
- 238000000034 method Methods 0.000 title claims abstract description 42
- 239000010409 thin film Substances 0.000 title claims abstract description 16
- 230000001590 oxidative effect Effects 0.000 claims abstract description 32
- 238000001035 drying Methods 0.000 claims abstract description 13
- 238000000137 annealing Methods 0.000 claims abstract description 10
- 239000002904 solvent Substances 0.000 claims description 22
- 238000009987 spinning Methods 0.000 claims description 21
- 239000007800 oxidant agent Substances 0.000 claims description 20
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 13
- 239000001301 oxygen Substances 0.000 claims description 13
- 229910052760 oxygen Inorganic materials 0.000 claims description 13
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 8
- 239000010408 film Substances 0.000 claims description 8
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 6
- 229910052719 titanium Inorganic materials 0.000 claims description 6
- 239000010936 titanium Substances 0.000 claims description 6
- 229910052726 zirconium Inorganic materials 0.000 claims description 6
- 229910052746 lanthanum Inorganic materials 0.000 claims description 3
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 3
- 239000011324 bead Substances 0.000 description 26
- 239000000243 solution Substances 0.000 description 21
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 6
- XPGAWFIWCWKDDL-UHFFFAOYSA-N propan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCC[O-].CCC[O-].CCC[O-].CCC[O-] XPGAWFIWCWKDDL-UHFFFAOYSA-N 0.000 description 5
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- 229940046892 lead acetate Drugs 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 3
- KQNKJJBFUFKYFX-UHFFFAOYSA-N acetic acid;trihydrate Chemical compound O.O.O.CC(O)=O KQNKJJBFUFKYFX-UHFFFAOYSA-N 0.000 description 3
- 238000005266 casting Methods 0.000 description 3
- 238000010981 drying operation Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- AZJLMWQBMKNUKB-UHFFFAOYSA-N [Zr].[La] Chemical compound [Zr].[La] AZJLMWQBMKNUKB-UHFFFAOYSA-N 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- HFGPZNIAWCZYJU-UHFFFAOYSA-N lead zirconate titanate Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ti+4].[Zr+4].[Pb+2] HFGPZNIAWCZYJU-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000003039 volatile agent Substances 0.000 description 2
- 230000001133 acceleration Effects 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- YRKCZRMEPGLHRN-UHFFFAOYSA-K lanthanum(3+);triacetate;hydrate Chemical compound O.[La+3].CC([O-])=O.CC([O-])=O.CC([O-])=O YRKCZRMEPGLHRN-UHFFFAOYSA-K 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/324—Thermal treatment for modifying the properties of semiconductor bodies, e.g. annealing, sintering
-
- H01L27/20—
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
- H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
- H01L21/02172—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides
- H01L21/02175—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides characterised by the metal
- H01L21/02186—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides characterised by the metal the material containing titanium, e.g. TiO2
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
- H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
- H01L21/02172—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides
- H01L21/02175—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides characterised by the metal
- H01L21/02189—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides characterised by the metal the material containing zirconium, e.g. ZrO2
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
- H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
- H01L21/02172—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides
- H01L21/02175—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides characterised by the metal
- H01L21/02192—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides characterised by the metal the material containing at least one rare earth metal element, e.g. oxides of lanthanides, scandium or yttrium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
- H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
- H01L21/02172—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides
- H01L21/02175—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides characterised by the metal
- H01L21/02194—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides characterised by the metal the material containing more than one metal element
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
- H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
- H01L21/02172—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides
- H01L21/02197—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides the material having a perovskite structure, e.g. BaTiO3
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02225—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer
- H01L21/0226—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process
- H01L21/02282—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process liquid deposition, e.g. spin-coating, sol-gel techniques, spray coating
-
- H01L41/1875—
-
- H01L41/318—
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N30/00—Piezoelectric or electrostrictive devices
- H10N30/01—Manufacture or treatment
- H10N30/07—Forming of piezoelectric or electrostrictive parts or bodies on an electrical element or another base
- H10N30/074—Forming of piezoelectric or electrostrictive parts or bodies on an electrical element or another base by depositing piezoelectric or electrostrictive layers, e.g. aerosol or screen printing
- H10N30/077—Forming of piezoelectric or electrostrictive parts or bodies on an electrical element or another base by depositing piezoelectric or electrostrictive layers, e.g. aerosol or screen printing by liquid phase deposition
- H10N30/078—Forming of piezoelectric or electrostrictive parts or bodies on an electrical element or another base by depositing piezoelectric or electrostrictive layers, e.g. aerosol or screen printing by liquid phase deposition by sol-gel deposition
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N30/00—Piezoelectric or electrostrictive devices
- H10N30/80—Constructional details
- H10N30/85—Piezoelectric or electrostrictive active materials
- H10N30/853—Ceramic compositions
- H10N30/8548—Lead-based oxides
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N30/00—Piezoelectric or electrostrictive devices
- H10N30/80—Constructional details
- H10N30/85—Piezoelectric or electrostrictive active materials
- H10N30/853—Ceramic compositions
- H10N30/8548—Lead-based oxides
- H10N30/8554—Lead-zirconium titanate [PZT] based
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N39/00—Integrated devices, or assemblies of multiple devices, comprising at least one piezoelectric, electrostrictive or magnetostrictive element covered by groups H10N30/00 – H10N35/00
Definitions
- This invention relates to the field of integrated circuits. More particularly, this invention relates to ferroelectric layers in integrated circuits.
- An integrated circuit may include components with a ferroelectric thin film, such as lead zirconium titanate or lead lanthanum zirconium titanate.
- Ferroelectric thin films may be used, for example, as dielectric layers in capacitors of non-volatile memory cells.
- Ferroelectric thin films may be formed from a sol gel solution, which is a mixture of metal-organic chemicals in solvent. Forming ferroelectric thin films from sol gel solutions with desired structural integrity, thickness, breakdown voltage, leakage current density may be problematic.
- An integrated circuit containing a ferroelectric film may be formed by a process including dispensing sol gel solution onto a wafer which will contain the integrated circuit to form a sol gel layer, spinning the wafer to distribute the sol gel solution so as to form a sol gel layer, and drying the sol gel layer so as to prevent radial edge spikes.
- the sol gel layer is baked in a non-reducing ambient so that temperature increases with time during the bake so as to remove at least 90 percent of organics from the sol gel layer. These steps may be repeated to form a thicker sol gel layer.
- the sol gel layer is annealed in an oxidizing ambient by a process including an initial ramped bake to remove residual volatiles, a crystallization anneal at high pressure in an oxidizing ambient while spinning the wafer, followed by a second crystallization anneal at low pressure and high ambient flow while spinning the wafer, followed by a temperature ramp down step.
- FIG. 1 is a flowchart of a process of forming an integrated circuit containing a ferroelectric film.
- FIG. 2 depicts a wafer in a spin coat apparatus for forming a sol gel layer on the wafer.
- FIG. 3 is a flowchart of a process to form the sol gel layer on the top surface of the wafer as depicted in FIG. 2 .
- FIG. 4 depicts the wafer in an edge bead removal apparatus, which may possibly be the spin coat apparatus of FIG. 2 .
- FIG. 5 is a flowchart of an edge bead removal process performed in the edge bead removal apparatus of FIG. 4 .
- FIG. 6 is a flowchart of a sol gel layer dry process performed in the edge bead removal apparatus of FIG. 4 .
- FIG. 7 depicts the wafer in a sol gel layer bake apparatus.
- FIG. 8A and FIG. 8B are flowcharts of exemplary embodiments of a sol gel layer bake process performed in the sol gel layer bake apparatus of FIG. 7 .
- FIG. 9 depicts the wafer in a sol gel layer anneal apparatus.
- FIG. 10 is a flowchart of an exemplary sol gel anneal process performed in the sol gel layer anneal apparatus of FIG. 9 .
- percent relative humidity is understood to mean a percentage of water vapor relative to a saturated ambient, at a specified temperature. For example, an ambient with 100 percent relative humidity at 25° C. would have 23.76 torr water vapor pressure, which corresponds to 23.0 grams of water per cubic meter of ambient. Similarly, an ambient with 1 percent relative humidity at 25° C. would have 0.24 torr water vapor pressure, which corresponds to 0.23 grams of water per cubic meter of ambient.
- An integrated circuit containing a ferroelectric film may be formed by a process including dispensing sol gel solution onto a wafer which will contain the integrated circuit to form a sol gel layer, spinning the wafer to distribute the sol gel solution so as to form a sol gel layer, performing an edge bead removal process using an edge bead removal solvent which is immiscible in the sol gel layer, and drying the sol gel layer so as to prevent radial edge spikes.
- the sol gel layer is baked in a non-reducing ambient so that temperature increases with time during the bake so as to remove at least 90 percent of organics from the sol gel layer. These steps may be repeated to form a thicker sol gel layer.
- the sol gel layer is annealed by a process including an initial ramped bake in an oxidizing ambient to remove volatiles, a crystallization anneal at high pressure in an oxidizing ambient while spinning the wafer, followed by a second crystallization anneal at low pressure and high ambient flow while spinning the wafer, followed by a temperature ramp down step.
- Sol gel solution is a mixture of metal-organic chemicals in solvent.
- a sol gel solution used to form a lead zirconium titanate (PZT) ferroelectric thin film may start with lead acetate trihydrate, titanium isopropoxide, zirconium n-propoxide, and 2-methoxyethanol solvent.
- the sol gel solution might be prepared by drying the lead acetate trihydrate and mixing it with a portion of the 2-methoxyethanol followed by heating, while separately mixing the titanium isopropoxide and zirconium n-propoxide with another portion of the 2-methoxyethanol followed by heating, and subsequently mixing the lead acetate mixture with the titanium isopropoxide and zirconium n-propoxide mixture, followed by dilution with organic solvents. Relative amounts of the titanium isopropoxide and zirconium n-propoxide may be adjusted to provide a desired ratio of titanium to zirconium in the PZT ferroelectric thin film.
- a sol gel solution used to form a lead lanthanum zirconium titanate (PLZT) ferroelectric thin film may start with lanthanum acetate hydrate in addition to lead acetate trihydrate, titanium isopropoxide and zirconium n-propoxide.
- the sol gel solution may include excess lead, possibly 10 percent excess, to compensate for lead loss during the anneal operation.
- Sol gel solutions prepared by other means are within the scope of the instant invention. Sol gel solutions are commercially available having relative concentrations of metals to provide a desired stoichiometry of the ferroelectric thin film.
- FIG. 1 is a flowchart of a process of forming an integrated circuit containing a ferroelectric film.
- the process 100 begins with step 102 to form a sol gel layer on a wafer which will contain the integrated circuit. Details of step 102 will be discussed in reference to FIG. 2 and FIG. 3 .
- step 104 is to perform an edge bead removal operation on the sol gel layer, in which sol gel material is removed from an edge of the wafer. Details of step 104 will be discussed in reference to FIG. 4 and FIG. 5 .
- step 106 is to dry the sol gel layer, so as to remove a portion of solvents from the sol gel layer. Details of drying the sol gel layer will be discussed in reference to FIG. 4 and FIG. 6 .
- step 108 is to bake the sol gel layer so as to remove at least 90 percent of remaining solvents from the sol gel layer. Details of baking the sol gel layer are discussed in reference to FIG. 7 and FIG. 8 .
- Steps 102 through 108 may be repeated to form a thicker sol gel layer, as depicted in FIG. 1 by step 110 .
- a second sol gel layer is formed by dispensing a second portion of sol gel solution on a top surface of the first sol gel layer and repeating steps 102 through 108 .
- steps 102 through 108 may be performed between five and twelve times.
- step 112 is to anneal the sol gel layer to form a crystalline ferroelectric thin film. Details of annealing the sol gel layer are discussed in reference to FIG. 9 and FIG. 10 .
- FIG. 2 depicts a wafer in a spin coat apparatus for forming a sol gel layer on the wafer.
- the wafer 200 is disposed in the spin coat apparatus 202 on a rotating chuck 204 capable of spinning the wafer 200 up to several thousand revolutions per minute (rpm).
- the spin coat apparatus 202 includes a sol gel dispense head 206 which delivers sol gel solution to a top surface of the wafer 200 , as depicted schematically in FIG. 2 by a dispensed sol gel dose 208 .
- the spin coat apparatus 202 may include a spinner bowl 210 to control excess sol gel solution.
- the dispensed sol gel solution on the top surface of the wafer 200 is distributed over the top surface of the wafer by rotating the chuck 204 to form a sol gel layer 212 .
- FIG. 3 is a flowchart of a process to form the sol gel layer on the top surface of the wafer as depicted in FIG. 2 .
- the sol gel layer forming process 300 begins with step 302 to dispense a portion of the sol gel solution 208 onto the top surface of the wafer 200 .
- 2 cm 3 of sol gel solution 208 may be dispensed onto a 200 mm wafer 200 .
- the chuck 204 may spin the wafer 200 between 500 rpm and 1500 rpm as the sol gel solution 208 is dispensed.
- step 304 is to spin the wafer to form the sol gel layer 212 on the top surface of the wafer 200 with a thickness in a desired range.
- a 200 mm wafer 200 may be spun between 1500 rpm and 3500 rpm to form the sol gel layer 212 .
- Spin speeds and accelerations in step 304 may be selected to provide a desired thickness and uniformity while avoiding radial striations.
- Step 304 may be referred to as a casting operation.
- a portion of solvents in the sol gel layer 212 may be removed during the casting operation.
- water vapor in an ambient over the wafer 200 may react with the sol gel layer 212 in a gelation reaction to form a gel.
- FIG. 4 depicts the wafer 200 in an edge bead removal apparatus 400 , which may possibly be the spin coat apparatus 202 of FIG. 2 .
- the wafer 200 with the sol gel layer 212 is disposed in the edge bead removal apparatus 400 on a rotating chuck 402 , which may be the chuck 204 in the spin coat apparatus 202 .
- the edge bead removal apparatus 400 includes an edge bead removal solvent dispense head 404 which delivers edge bead removal solvent to an outer edge of the wafer 200 as the wafer 200 is rotated, as depicted schematically in FIG. 4 by dispensed edge bead removal solvent 406 .
- the edge bead removal apparatus 400 may include a spinner bowl 408 to collect edge bead removal solvent.
- a drying operation is also performed in the edge bead removal apparatus 400 to remove more solvent from the sol gel layer 212 .
- the wafer 200 is spun, for example between 800 rpm and 2500 rpm for a 200 mm wafer 200 .
- a non-reducing ambient is provided over the sol gel layer 212 during the drying operation.
- FIG. 5 is a flowchart of an edge bead removal process 500 performed in the edge bead removal apparatus 400 of FIG. 4 .
- the edge bead removal process 500 begins with step 502 to adjust the spin speed of the wafer 200 .
- step 504 is to dispense edge bead removal solvent 406 from the solvent dispense head 404 onto the outer edge of the wafer 200 .
- the dispensed edge bead removal solvent 406 removes sol gel material from an edge band, commonly between 2 and 10 mm wide, at the outer edge of the wafer 200 .
- the edge bead removal solvent 406 is selected to be immiscible in the sol gel material.
- the edge bead removal solvent 406 may be at least 99 percent water.
- a spin speed of the wafer is selected to provide adequate removal of the sol gel material without undercutting the sol gel layer 212 .
- a 200 mm wafer 200 may be spun between 1500 rpm and 3000 rpm while the edge bead removal solvent 406 is dispensed.
- FIG. 6 is a flowchart of a sol gel layer dry process 600 performed in the edge bead removal apparatus 400 of FIG. 4 .
- the dry process 600 begins with step 602 to adjust the spin speed of the wafer 200 .
- step 604 is to spin the wafer 200 in the non-reducing ambient for at least 5 seconds.
- the non-reducing ambient in the dry process 600 has at least 1 percent relative humidity at 25° C.
- a flow rate of the non-reducing ambient may be between 300 cm 3 /minute and 1000 cm 3 /minute.
- the non-reducing ambient may include at least 1 percent oxygen.
- the non-reducing ambient may include at least 20 percent oxygen.
- the spin speed of a 200 mm wafer 200 during step 604 may be between 800 rpm and 2500 rpm.
- a further portion of solvent in the sol gel layer 212 may be removed during step 604 .
- Oxidizing agents in the ambient may react with the sol gel layer 212 to form more gel.
- FIG. 7 depicts the wafer 200 in a sol gel layer bake apparatus 700 .
- the wafer 200 with the sol gel layer 212 is disposed on a bake chuck 702 .
- Heat is applied to the wafer 200 , for example by heating the bake chuck 702 with a heater element 704 as depicted in FIG. 7 .
- Other means of heating the wafer 200 are within the scope of the instant embodiment.
- the sol gel layer bake apparatus 700 includes a bake chamber 706 with an inlet port 708 and an outlet port 710 .
- a non-reducing ambient, not shown, is provided in the bake chamber 706 by delivering non-reducing gas through the inlet port 708 and extracting it through the outlet port 710 .
- a sol gel bake process is performed prior to annealing the sol gel layer.
- the bake process is performed in a non-reducing ambient so that a temperature of the sol gel layer 212 increases from a starting temperature between 100° C. and 225° C. to a final temperature between 275° C. and 425° C. and extends at least 2 minutes.
- the bake process is performed so that at least 90 percent of solvent in the sol gel layer 212 is removed at a rate which does not introduce defects or voids in the sol gel layer 212 .
- the non-reducing ambient may include at least 1 percent oxygen.
- a first exemplary sol gel layer bake process 800 begins with step 802 to bake the sol gel layer 212 at a temperature between 100° C. and 225° C. for a time between 2 and 10 minutes in a non-reducing ambient.
- step 804 is to bake the sol gel layer 212 at a temperature between 250° C. and 350° C. for a time between 2 and 10 minutes in a non-reducing ambient.
- a second exemplary sol gel layer bake process 806 begins with step 808 to bake the sol gel layer 212 at a temperature between 100° C. and 125° C. for a time between 4 and 7 minutes in an oxygen ambient.
- step 810 is to bake the sol gel layer 212 at a temperature between 225° C. and 275° C. for a time between 4 and 7 minutes in an oxygen ambient.
- step 812 is to bake the sol gel layer 212 at a temperature between 325° C. and 425° C. for a time between 4 and 7 minutes in an oxygen ambient.
- FIG. 9 depicts the wafer 200 in a sol gel layer anneal apparatus 900 .
- the wafer 200 is disposed over a rotating chuck 902 , possibly on standoff pins 904 .
- the anneal apparatus 900 includes an anneal chamber 906 with an inlet port 908 and an outlet port 910 .
- An oxidizing ambient is provided in the bake chamber 906 by delivering oxidizing gas through the inlet port 708 and extracting it through the outlet port 910 .
- Heating means 912 for example one or more heating lamps 912 as depicted in FIG. 9 , are disposed in the anneal chamber 906 .
- FIG. 10 is a flowchart of an exemplary sol gel anneal process 1000 performed in the sol gel layer anneal apparatus 900 of FIG. 9 , to be performed in the order depicted in FIG. 10 .
- the anneal process 1000 begins with step 1002 to bake the wafer 200 and sol gel layer 212 at a temperature between 250° C. and 350° C. for at least 30 seconds while ramping a pressure of the oxidizing ambient from less than 100 torr to between 700 torr and 1000 torr at a ramp rate greater than 10 torr per second while flowing an oxidant in the ambient between 3 and 7 standard liters per minute (slm).
- the pressure of the oxidizing ambient may be ramped at a ramp rate greater than 25 torr per second.
- the ambient includes at least 95 percent oxygen.
- the ambient includes at least 99 percent oxygen.
- the wafer may be spun during step 1002 , for example between 50 and 125 rpm.
- Step 1004 is to ramp up the temperature of the wafer 200 and sol gel layer 212 to between 425° C. and 475° C. over a time period of at least 20 seconds while the ambient pressure is maintained between 700 torr and 1000 torr and the flow rate of the oxidant in the ambient is maintained between 3 and 7 slm.
- the wafer may be spun during step 1004 , for example between 50 and 125 rpm.
- Step 1006 is to bake the wafer 200 and sol gel layer 212 at a temperature between 475° C. and 525° C. for at least 30 seconds while the ambient pressure is maintained between 700 torr and 1000 torr and the flow rate of the oxidant in the ambient is maintained between 3 and 7 slm.
- the wafer may be spun during step 1006 , for example between 50 and 125 rpm.
- Step 1008 is to ramp up the temperature of the wafer 200 and sol gel layer 212 to between 650° C. and 750° C. at a ramp rate between 20 and 60 degrees C. per minute while the ambient pressure is maintained between 700 torr and 1000 torr and the flow rate of the oxidant in the ambient is maintained between 3 and 7 slm.
- the wafer may be spun during step 1006 , for example between 50 and 125 rpm.
- Step 1010 is to anneal the wafer 200 and sol gel layer 212 at a temperature between 650° C. and 750° C. for at least 60 seconds while spinning the wafer 200 between 50 and 125 rpm and while the ambient pressure is maintained between 700 torr and 1000 torr and the flow rate of the oxidant in the ambient is maintained between 3 and 7 slm.
- Step 1012 is to anneal the wafer 200 and sol gel layer 212 at a temperature between 650° C. and 750° C. for at least 20 seconds while spinning the wafer 200 between 50 and 125 rpm and while the ambient pressure is maintained between 4 torr and 10 torr and the flow rate of the oxidant in the ambient is at least 5 slm.
- Step 1014 is to ramp down the temperature of the wafer 200 and sol gel layer 212 at a ramp rate greater than 5 degrees C. per second to a temperature below 475° C. while spinning the wafer 200 between 50 and 125 rpm and while the ambient pressure is maintained between 4 torr and 10 torr and the flow rate of the oxidant in the ambient is at least 5 slm.
- the temperature of the wafer 200 and sol gel layer 212 may be ramped down at a ramp rate between 10 degrees C. per second and 25 degrees C. per second.
- a sol gel layer may be annealed in a furnace, so that all the steps of the process 1000 described in reference to FIG. 10 are performed without spinning the wafer.
- a PLZT thin film with a lead:lanthanum ratio of 93:7 and a zirconium:titanium ratio of 58:42 may be formed according the embodiment described herein to have a thickness of 400 nanometers of at least 99 percent perovskite phase, with a dielectric constant above 1400, a breakdown voltage above 150 volts and a leakage current density less than 10 ⁇ 7 amps/cm 2 .
Landscapes
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Microelectronics & Electronic Packaging (AREA)
- General Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Computer Hardware Design (AREA)
- Physics & Mathematics (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Ceramic Engineering (AREA)
- Dispersion Chemistry (AREA)
- Materials Engineering (AREA)
- Semiconductor Memories (AREA)
- Formation Of Insulating Films (AREA)
Abstract
Description
Claims (11)
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US13/340,093 US9005698B2 (en) | 2010-12-29 | 2011-12-29 | Piezoelectric thin film process |
US14/684,663 US9728423B2 (en) | 2010-12-29 | 2015-04-13 | Piezoelectric thin film process |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US201061427973P | 2010-12-29 | 2010-12-29 | |
US13/340,093 US9005698B2 (en) | 2010-12-29 | 2011-12-29 | Piezoelectric thin film process |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US14/684,663 Continuation US9728423B2 (en) | 2010-12-29 | 2015-04-13 | Piezoelectric thin film process |
Publications (2)
Publication Number | Publication Date |
---|---|
US20120171364A1 US20120171364A1 (en) | 2012-07-05 |
US9005698B2 true US9005698B2 (en) | 2015-04-14 |
Family
ID=46380990
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US13/340,093 Active 2033-05-17 US9005698B2 (en) | 2010-12-29 | 2011-12-29 | Piezoelectric thin film process |
US14/684,663 Active 2032-03-20 US9728423B2 (en) | 2010-12-29 | 2015-04-13 | Piezoelectric thin film process |
Family Applications After (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US14/684,663 Active 2032-03-20 US9728423B2 (en) | 2010-12-29 | 2015-04-13 | Piezoelectric thin film process |
Country Status (1)
Country | Link |
---|---|
US (2) | US9005698B2 (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20150214069A1 (en) * | 2010-12-29 | 2015-07-30 | Texas Instruments Incorporated | Piezoelectric thin film process |
US20180351010A1 (en) * | 2015-11-23 | 2018-12-06 | Council Of Scientific & Industrial Research | Preparation of anti-reflection and passivation layers of silicon surface |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US10232336B2 (en) * | 2013-11-06 | 2019-03-19 | The Charles Stark Draper Laboratory, Inc. | Systems and method for high-throughput testing |
US10354858B2 (en) * | 2013-12-31 | 2019-07-16 | Texas Instruments Incorporated | Process for forming PZT or PLZT thinfilms with low defectivity |
JP7019400B2 (en) * | 2017-12-15 | 2022-02-15 | キヤノン株式会社 | Manufacturing method of membrane and liquid discharge head |
US11832520B2 (en) * | 2021-04-27 | 2023-11-28 | Taiwan Semiconductor Manufacturing Company, Ltd. | Voltage breakdown uniformity in piezoelectric structure for piezoelectric devices |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5028455A (en) * | 1987-06-02 | 1991-07-02 | National Semiconductor Corporation | Method for preparing plzt, pzt and plt sol-gels and fabricating ferroelectric thin films |
US5728626A (en) * | 1993-07-26 | 1998-03-17 | At&T Global Information Solutions Company | Spin-on conductor process for integrated circuits |
US20040129918A1 (en) * | 2002-09-20 | 2004-07-08 | Canon Kabushiki Kaisha | Composition for forming piezoelectric film, producing method for piezoeletric film, piezoeletric element and ink jet recording head |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US9005698B2 (en) * | 2010-12-29 | 2015-04-14 | Texas Instruments Incorporated | Piezoelectric thin film process |
-
2011
- 2011-12-29 US US13/340,093 patent/US9005698B2/en active Active
-
2015
- 2015-04-13 US US14/684,663 patent/US9728423B2/en active Active
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5028455A (en) * | 1987-06-02 | 1991-07-02 | National Semiconductor Corporation | Method for preparing plzt, pzt and plt sol-gels and fabricating ferroelectric thin films |
US5728626A (en) * | 1993-07-26 | 1998-03-17 | At&T Global Information Solutions Company | Spin-on conductor process for integrated circuits |
US20040129918A1 (en) * | 2002-09-20 | 2004-07-08 | Canon Kabushiki Kaisha | Composition for forming piezoelectric film, producing method for piezoeletric film, piezoeletric element and ink jet recording head |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20150214069A1 (en) * | 2010-12-29 | 2015-07-30 | Texas Instruments Incorporated | Piezoelectric thin film process |
US9728423B2 (en) * | 2010-12-29 | 2017-08-08 | Texas Instruments Incorporated | Piezoelectric thin film process |
US20180351010A1 (en) * | 2015-11-23 | 2018-12-06 | Council Of Scientific & Industrial Research | Preparation of anti-reflection and passivation layers of silicon surface |
US10811546B2 (en) * | 2015-11-23 | 2020-10-20 | Council Of Scientific & Industrial Research | Preparation of anti-reflection and passivation layers of silicon surface |
Also Published As
Publication number | Publication date |
---|---|
US9728423B2 (en) | 2017-08-08 |
US20120171364A1 (en) | 2012-07-05 |
US20150214069A1 (en) | 2015-07-30 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US9728423B2 (en) | Piezoelectric thin film process | |
TWI588895B (en) | Method for manufacturing ferroelectric thin film | |
JP3113141B2 (en) | Ferroelectric crystal thin film coated substrate, method of manufacturing the same, and ferroelectric thin film device using ferroelectric crystal thin film coated substrate | |
TWI613725B (en) | Method for manufacturing ferroelectric thin film | |
TWI586628B (en) | Production method of lead zirconium titanate (PZT) based dielectric thin film | |
EP1846344B1 (en) | Method of preparing oxide ceramic based on lead, titanium, zirconium and lanthanide(s) | |
CN108352443A (en) | The forming method of PZT ferroelectric films | |
KR20140117262A (en) | METHOD OF FORMING PNbZT FERROELECTRIC THIN FILM | |
EP2450946B1 (en) | Method for removing ferroelectric csd coating film | |
TW201344724A (en) | Method of manufacturing ferroelectric thin film | |
JP2000154008A (en) | Method for producing ferroelectric thin film using sol-gel method | |
JP4042276B2 (en) | Method for forming Pb-based perovskite metal oxide thin film | |
JP5434631B2 (en) | CSD coating film removing composition, CSD coating film removing method using the same, ferroelectric thin film and method for producing the same | |
JP2006222136A (en) | Capacitor element manufacturing method, semiconductor device manufacturing method, and semiconductor manufacturing apparatus | |
JP6665673B2 (en) | Manufacturing method of ferroelectric thin film | |
JP5381410B2 (en) | Method for manufacturing ferroelectric thin film | |
JP6459563B2 (en) | PZT-based ferroelectric thin film and method for forming the same | |
TWI667201B (en) | Method of forming lanio3 thin film | |
JP2000001368A (en) | Ferroelectric thin film, stock solution for forming same and formation of same | |
JP2007246322A (en) | Metal oxide precursor solution, metal oxide film forming method, semiconductor device manufacturing method, and electronic device manufacturing method | |
JP2001002418A (en) | Composition for forming plcszt ferroelectric thin film and formation of plcszt ferroelectric thin film |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AS | Assignment |
Owner name: TEXAS INSTRUMENTS INCORPORATED, TEXAS Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:HAIDER, ASAD MAHMOOD;REEL/FRAME:027788/0778 Effective date: 20111229 |
|
STCF | Information on status: patent grant |
Free format text: PATENTED CASE |
|
MAFP | Maintenance fee payment |
Free format text: PAYMENT OF MAINTENANCE FEE, 4TH YEAR, LARGE ENTITY (ORIGINAL EVENT CODE: M1551); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY Year of fee payment: 4 |
|
MAFP | Maintenance fee payment |
Free format text: PAYMENT OF MAINTENANCE FEE, 8TH YEAR, LARGE ENTITY (ORIGINAL EVENT CODE: M1552); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY Year of fee payment: 8 |